JPS59190847A - Decorative sheet and manufacture of decorative material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a decorative sheet and decorative material having excellent impact resistance, bending resistance, heat resistance, adhesiveness, etc.

Conventionally, as a decorative sheet, a pattern layer and a white coating layer (hidden layer) were sequentially placed on one side of a plastic film.
Also known are those coated with an adhesive layer. Pressure-bond this decorative sheet to the base material to be laminated, -! The edges are applied by heat compression bonding. Alternatively, there is also known a method in which an adhesive layer is not provided as a decorative sheet, and when the decorative sheet is laminated to a base material, the adhesive is completely applied to the base material or the decorative sheet is pressed and bonded. The adhesive used here is an adhesive using a thermoplastic resin and a curable resin, and the decorative sheet is bonded by thermocompression bonding with an adhesive mainly composed of a thermoplastic resin. Examples of the thermoplastic resin include vinyl resin, acrylic resin, polyamide resin, and rubber resin. Decorative sheets laminated using adhesives mainly composed of thermoplastic resins generally have poor heat resistance and solvent resistance, and furthermore, adhesive properties are not necessarily sufficient. Therefore, the reality is that its use in substrates that require good physical properties, such as metal surfaces, is limited.

In addition, adhesives using curable resins do not have sufficient storage stability as decorative sheets, and decorative sheets with adhesives 1
- Must be laminated to the i-substrate before the adhesive hardens. Therefore, the reality is that they generally do not have a long shelf life. As this curable resin, urethane resin or the like is used.

Furthermore, the decorative materials obtained using these decorative sheets have the disadvantage that they do not have sufficient impact resistance or bending resistance.

Note that a transfer painting method disclosed in Japanese Patent Application Laid-Open No. 57-49591 is also known. Although this method has the advantage of excellent workability, it involves the work of completely peeling off the base sheet (plastic film), and the plastic film that is the base sheet is generally difficult to reuse, so it ends up being discarded. However, the cost of plastic and film is relatively high in the decorative sheet, and as a result, this transfer method poses a cost problem.

The present invention uses a plastic film as an intermediate layer,
Furthermore, the present invention relates to a method for producing decorative sheets and decorative materials that have excellent heat resistance, adhesiveness, impact resistance, and bending resistance by using a radiation-curable adhesive layer.

That is, it is a cosmetic notebook consisting of a protective coating layer, a pattern layer, an adhesive layer if necessary, a plastic, a film, and a radiation-curable adhesive layer.

Furthermore, a protective coating layer, a pattern layer, an adhesive layer if necessary,
and a plastic film surface made of a plastic film is laminated to a base material via a radiation-curable adhesive layer,
This is a method for producing decorative materials that is cross-linked and cured by radiation irradiation.

The basic composition of the decorative sheet of the present invention is a protective layer/picture layer/plastic film/radiation-curable adhesive layer, and a protective layer/picture layer/adhesive layer/plasti, film/radiation-curable adhesive layer. be. In addition to this basic configuration, a decorative sheet may have a configuration in which about 1 to 3 layers of a concealing layer and other adhesive layers are added. For example, protective layer/picture layer/hidden layer/plastic film/radiation-curable adhesive layer, protective layer/picture layer/adhesive layer/plastic film/adhesive layer/hidden layer/radiation-curable adhesive layer, etc. be. In addition,
In the production of decorative materials, the radiation-curable adhesive layer may not be formed on a decorative sheet, but may be coated on a base material and bonded.

As plastic and film, it has impact resistance, bending resistance,
A film with excellent heat resistance is preferred.

For example, various plastic films such as polyester film (polyethylene terephthalate film), nylon film, polyethylene film, polypropylene film, and polyvinyl butyral film can be used.

The plastic film may be transparent, or it may also be a colored film containing pigments, or a film on which a thin film of metal or metal oxide is formed by vapor deposition, thinning, or taring. By using these films, they can also serve as a concealing layer, and in some cases, they can also be expected to improve adhesion.

A pattern layer and a protective coating layer are formed on one side of the plastic film via an adhesive layer, if necessary. As for this adhesive layer, the pattern layer and the protective coating layer are plastic,
If the composition has good adhesion to the film, it can be omitted.

This adhesive layer is formed of an adhesive mainly composed of a thermoplastic resin, or a urethane-curing, thermosetting, or radiation-curing adhesive. In some cases, two or more layers may be combined to form a coating.

Examples of curable resins and thermoplastic resins include unsaturated polyester resins, epoxy resins, urethane resins, urea resins, melamine resins, alkyd resins, acrylic resins, polyamides, urethane-modified epoxy resins, vinyl chloride resins, and thermoplastic polyester resins. etc., and is applied as a coating composition onto plasti, along with a solvent and various additives. In addition, when a thermosetting grade 1 resin is used, it is thermosetted during the production of the decorative sheet or before or after the radiation irradiation after the decorative sheet is attached.

Furthermore, this adhesive layer may be a radiation-curable adhesive described later. That is, it contains a monomer having an ethylenically unsaturated double bond and a fiber or a prepolymer.

As the pattern layer, a printed layer formed by various types of printing such as gravure printing, offset printing, flexographic printing, and letterpress printing, or a pattern layer formed by partial metal vapor deposition can be used. In the case of the printing layer, various conventionally used inks can be used as printing inks, and radiation-curable inks may also be used.

The pattern layer can be formed on the adhesive layer, plastic, or film by various printing methods such as gravure printing, offset printing, and screen/printing. Alternatively, the pattern layer can be provided by a conventionally known metal vapor deposition method, and may be partially vapor deposited or a combination of printing and vapor deposition.

The protective coating layer allows the pattern layer to be seen through, and is formed on the pattern layer using various coating methods using thermoplastic resin, radiation curing resin, or other curable resin. Since the protective coating layer often requires solvent resistance, heat resistance, and strength, a flexible radiation-curing resin is used. Since thermocompression bonding is often used when press-bonding a twisted substrate to a substrate, it is preferable that a curable resin is used as a protective coating layer to be previously cured before being press-bonded. As the radiation-curable resin, the composition used for the radiation-curable adhesive layer described later can be used in the same manner. By making the protective coating layer also radiation-curable, the protective coating layer and the radiation-curable adhesive layer can be cured by a single radiation irradiation.

Examples of other curable resins and thermoplastic resins include unsaturated polyester resins, epoxy resins, urethane resins, urea resins, melamine resins, alky, acrylic resins, polyamides, urethane-modified epoxy resins, Vinyl chloride resin, thermoplastic polyester 1￥jt Jljg
etc., and as a coating composition together with a solvent and various additives,
Painted on top of the pattern layer. In addition, when a thermosetting resin is used as the resin for the protective coating layer, during the manufacturing process of the decorative sheet -! The material is then thermally cured, or after pre-curing of radiation. -! Further, if necessary, after coating the entire protective coating layer, preliminary drying can be performed.

As the radiation-curable adhesive layer, a prepolymer having at least one ethylenically unsaturated bond and a 11v monomer are used. Examples of prepolymers include polyester acrylate, epoxy acrylate, urethane acrylate-1, polyether acrylate, polyol acrylate, melamine acrylate, polyester methacrylate-1, epoxy methacrylate-1, urethane methacrylate, and polyether methacrylate. ), polyol methacrylate 1-, melamine methacrylate,
Unsaturated polyester resin, etc.

Examples of monomers include ethylene glycol diacrylate, propylene glycol dibucryl-1-1
1,6-hexanethiol diacrylate 1., diethyl glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate 1.
, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylol propane l-'J methacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, etc. .

In addition to the prepolymer and monomer, organic solvents, polymerization inhibitors, pigments, etc. may be added as necessary to the radiation-curable resin composition to make a coating composition suitable for various small and wide applications. I can do it. In the present invention, in order to maintain good adhesion to the object to be laminated, for example, a metal surface, a radiation-cured resin composition containing a prepolymer as a main component and using no 7-mer or a small amount of 7-mer is used. 3. A very clever prepolymer and a flexible monomer of 10 to 90% by weight and a polymer having no ethylenically unsaturated bond of 10 to 90%
Compositions consisting of 90% by weight are also effective. Polymers without ethylenically unsaturated bonds include acrylic resin,
Polyamide resin, polyester resin, urethane resin, cellulose toilet fat, epoxy resin, vinyl acetate resin, vinyl chloride resin, butyral resin, poval resin, synthetic rubber,
These include ethylene-vinyl acetate stool fat. After coating this adhesive layer, it can be pre-dried to remove the solvent if necessary.

In the present invention, other adhesive layers are used as necessary, but for example, when the adhesion between the plastic film and the radiation-curable adhesive is not necessarily sufficient, the adhesive layer may be formed by thermoplastic resin or urethane-curable resin. agent is used.

-! Further, the hiding layer is also normally used as a layer below the pattern layer, but an adhesive layer, plastic, or film can also serve as the hiding layer. However, a separate hiding layer can also be inserted. This hiding layer is inserted between the pattern layer and the radiation-curable adhesive layer.

The hiding layer may be a colored coating layer, a metal thin film layer, or a combination thereof.

The Me coating layer is generally white (white coating layer), but may be a coating layer of other hues. The type of resin for the coating layer is preferably a curable resin, such as a thermosetting or radiation curing type. The coating layer is formed by printing or painting the entire surface with ink or paint. If it contains a solvent, pre-dry it. In the case of thermosetting, curing may be performed after printing or painting, or after the decorative sheet is manufactured or after the decorative sheet is bonded to the base material.

Next, a method for manufacturing a decorative material using the decorative sheet of the present invention will be explained.

The radiation-curable adhesive layer is pressed against the base material.

As an example of the pressure bonding method, the protective cover layer of the decorative sheet is pressure bonded to the base material using a press plate or a roll heated as necessary. The decorative sheet I received that does not have a radiation-curable adhesive layer has a radiation-curable adhesive layer on the base material,
If necessary, another adhesive layer is formed by coating, and a decorative sheet is laminated (thermo-press) thereon.

After crimping, irradiate with at least /1 radiation.

Radiation includes electron beams, X-rays, and gamma rays, but the desired 1L2
Another example is an electron beam. The scanning type electron beam accelerator is
Curtain type devices are known, but low accelerating voltage types may also be used. For example, the Electro Curtain type manufactured by Energy Sciences is preferably used, and the irradiation dose is usually 0.5.
~20M rad. Irradiation can also be carried out in an inert gas atmosphere. The base materials include iron plates, tin-free steel plates, zinc plates, copper plates, aluminum plates and other metal plates, metal containers such as cans, and containers.

These include plastic sheets, plastic, plastic containers, plastic molded products, paper, various types of wood, plywood, etc.

Next, the present invention will be explained by examples. “Part” in Examples
, ``person in charge'' refers to the person in charge of M and weight.

Example 1 Polyethylene terephthalate film (P) with a thickness of 12μ
30% by weight of methyl ethyl ketone and l-luene (]/1) solution of thermoplastic polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) was used as an adhesive layer on both sides of the ET film).
The film was coated uniformly using a roll coater to a film thickness of 5 μm on each side (dry film thickness, hereinafter the same). After coating, dry at 120℃ for 1 minute, remove the bath agent, and remove the adhesive layer on one side.
Then, an electron beam curable resin composition having the following composition was mixed with 20 parts of titanium oxide (anatase type) and 60 parts of methyl ethyl ketone using a roll coater.
] It was coated so that the thickness of O17 was uniform over the entire surface to form a white coat layer.

After coating, it was dried at 120°C for 1 minute to remove the bath agent.

Next, use gravure 1 ink to gravure print the pattern layer,
After drying at 80°C for 10 minutes, the following ultraviolet curable resin composition was mixed with polyester (Vylon 200).
1.0 part pentaerythritol triacrylate
5 parts benzoin ethyl ether
2 parts methyl ethyl ketone
25 parts toluene
It was coated uniformly over the entire surface to a thickness of 25 μm using a 25-part roll coater and dried at 120° C. for 1 minute to remove the solvent (formation of protective coating layer). From the coated surface, use an ozone-less type ultraviolet irradiation device at 80W/m (1 light), 5m/mi.
UV irradiation was carried out under curing conditions of n. On the other adhesive layer of It was made into a radiation-curable adhesive layer. After application, it was dried at 120° C. for 1 minute, and the bath agent was removed to prepare a decorative sheet.

Using the obtained decorative sheet, it was laminated on a tin-free steel plate using a laminator at 120° C. and bonded under heat. Next, using a curtain type energy science electron beam irradiation device under a nitrogen gas atmosphere from the protective coating layer side,
160KV.

It was cross-linked and cured by electron beam irradiation at a dose of 5 Mrad at 5 mA.

The decorative sheet had strong adhesion and was able to be cross-linked and cured on a T-free steel plate.

Test results and adhesion of the above-mentioned electron beam-cured decorative material (after diving): 100/10 in the Serono-Ntebugoban test.
0, which is good.

Boiling water resistance: As a result of immersion in boiling water at 100°C for 30 minutes,
Good with no change.

Solvent resistance: Good, withstands most solvents.

Refractive property: Withstands bending 2'A diameter.

Pencil hardness: 3H and showed good results.

Example 2 Each component layer was applied in the same manner as in Example 1, except that as a protective coating layer, a urethane two-component curable resin composition having the following composition was applied to Hytaloid 3206B (manufactured by Hitachi Chemical Co., Ltd.).
65 parts Methyl ethyl ketone 20 parts Coat the entire surface uniformly to a film thickness of 5μ using a roll coater, dry and cure at 120°C for 5 minutes, and then coat at 40°C.
After curing for 4 days, a decorative sheet was obtained.

This decorative sheet laminated sheet was pressed onto an aluminum plate using a laminator at 120° C. to laminate the decorative sheet. After lamination, the protective coating layer was irradiated with an electron beam at a dose of 5 M'rad under conditions similar to Example 1 in a nitrogen gas atmosphere to harden it.

The obtained decorative board had almost the same good quality as that of Example 1.

Example 3 The following composition was applied on one side of a PET film: Hythaloid 3206B 25 parts Coronate-L 5 parts Titanium oxide (Ryo Natase type) 25 parts Methyl ethyl ketone
A 45-part roll coater was used to uniformly coat the entire surface to a thickness of 10 μm to obtain a white coat layer. After coating and drying and curing at 150°C for 2 minutes, a pattern layer was formed thereon in the same manner as in Example 1.
Second, the urethane two-component curable resin paste used in Example 2 was applied] 7. A protective layer was formed, and curing was continued at 40° C. for 4 days.

On the other side of the PET film, an adhesive layer of Vylon 200 was formed in the same manner as in Example 1, and on top of it an electron beam curable resin composition of the following composition was added: 35 parts of Vylon 200, aloe, 5 parts of Kusu H-6400 Aloni, Kusu M-71005 parts Methyl ethyl ketone 30 parts Toluene
A radiation-curable adhesive layer was obtained by coating the entire surface with a 25-part roll coater to a uniform thickness of 5 μm. After application, it was dried at 120° C. for 1 minute to remove the solvent and prepare decorative sheet '1.

It was crimped onto a steel plate using a laminator under the same conditions as in Example 1, and was irradiated with an electron beam to harden it.

The obtained decorative material was almost the same as that of Example 1 and had good quality.

Example 4 The white coat layer shown in Example 3 was uniformly coated on both sides of a PET film using a roll coater so that the film thickness on one side was 5 μm. After coating, the coating was dried and cured at 150° C. for 2 minutes, and then a pattern layer was formed thereon in the same manner as in Example 1. Apply the two-component urethane curing resin of Example 2 on top of the pattern layer using a roll coater.
It was coated to a thickness of μ and dried and cured at 120° C. for 5 minutes to form a protective coating layer. On the other white coat layer, an electron beam curable adhesive composition having the same composition as in Example 1 was applied to a total thickness of 5 μm and dried to form a radiation curable adhesive layer.

The obtained decorative sheet was pressed onto a tin-free steel plate using a laminator under the same conditions as in Example 1, and was cured by electron beam irradiation.

The obtained decorative material was a good decorative sheet board.

Example 5 A white coat layer and a pattern layer were formed in the same manner as in Example 4, and a UV-curable resin layer having the composition shown in Example 1 was completely formed as a protective coating layer, and was irradiated with UV rays under the same conditions to cure. I let it happen.

An electron beam curable adhesive layer having the composition shown in Example 3 was formed to obtain a decorative sheet.

The obtained decorative sheet l- was laminated using the same method as in Example 1, thermocompression bonded onto an aluminum plate, and subjected to electron beam irradiation under the same conditions to obtain a good decorative sheet.Example 6 Oxidation A pattern layer and a protective coating layer were entirely formed in the same manner as in Example 1 on one side of a polyethylene phthalate film (thickness: 25 μm) containing 5 parts of titanium.

The following electron beam curable resin composition was applied onto the film surface of the other body: Vylon 200, 40 parts, methyl ethyl ketone, 25 parts toluene.
25 parts 20 - Coated uniformly over the entire surface to a thickness of 5 μm using a roll coater, dried at 120° C. for 1 minute, and completely removed the solvent to prepare a decorative sort.

Using the obtained 7V decorative sheet, it was laminated on a tin-free steel plate at 120°C with a laminator and bonded under heat. Next, from the coating layer side, a curtain method under a nitrogen gas atmosphere was applied. Using a radiation irradiation device, 15QI (V.

Electron beam irradiation was performed at a dose of 5 Mrad at 5 mA,
Hardened.

The decorative sheet had strong adhesive strength and could be cured and laminated onto the T-free steel plate.

As in Example 1, the test results of the above electron beam-cured decorative material showed good lamination properties, adhesion (after submersion), 1liI boiling water resistance, solvent resistance, refraction, and pencil hardness (on JHJd). The results were shown.

Example 7 The following composition was applied to both sides of a polypropylene film (25 μm thick) containing 5 parts by weight of titanium oxide.
JO part Toluene 90 parts Coated uniformly over the entire surface to a thickness of 3 μm using a roll coater (drying at 120° C. for 1 minute at -1 to remove the solvent (adhesive layer)).

A pattern layer was formed on this adhesive layer in the same manner as in Example 1.
A mining cover layer was formed. On the other blade side, Example 1 and m1
An electron beam curing adhesive having the same composition was formed and laminated on an aluminium plate under the same conditions.
It was cured by electron beam irradiation at a dose of d.

The obtained decorative board had almost the same good quality as that of Example 1.

Example 8 In the same manner as in Example, a pattern layer is formed, and a urethane-curing type urethane composition having the following composition is applied thereon to form Hytaloid 3206 B.
65 parts coronet 1-L
15 parts methyl ethyl ketone
The entire surface was uniformly coated using a 20-part roll coater to a film thickness of 5 μm. 120℃, 5 minutes n'A
After drying and curing, it was post-cured at 40° C. for 4 days (mining coating/!j).

A radiation-curable adhesive layer having the same composition as in Example 1 was applied onto the film surface on the other blade side and dried to obtain a decorative sheet. Using this decorative sheet, press it with a laminator at 1C 100℃ on a tin-free steel plate,
The entire surface of the y-retentive coating layer was irradiated with electron beams under the same conditions as in Example 1, and cured. The obtained f''l decorative board gave good results.

Example 9 A pattern layer was formed in the same manner as in Example 1 on a film in which aluminum was deposited on a polyethylene terephthalate film to a film thickness of 5ooX using a high-vacuum deposition apparatus manufactured by Nippon Shinku Gijutsu Co., Ltd., and the same mining coating was similarly applied. A layer was formed, exposed to UV light, and cured. On the other blade side, a 1:1 solution of methyl ethyl carbon/toluene (NV30
%) to a film thickness of 5 μm, dried at 120°C for 1 minute, and coated with an electron beam curable resin composition having the following composition: 25 parts of methyl ethyl ketone, 25 parts of toluene, using a roll coater to give a film thickness of 5 μm. Apply it evenly over the entire surface, and
It was dried at 20°C for 1 minute.

The obtained decorative sheet was laminated on an aluminum plate at 100° C., and was irradiated with an electron beam under the same conditions as in Example 1 to be cured. The resulting decorative material gave good results.

Example 10 A pattern layer was formed on a 25 μm thick polyethylene terephthalate film containing 31 ft% of phthalocyanine blue in the same manner as in Example 1, and an ultraviolet curable resin composition was applied thereon to a thickness of 5 μm. After drying, the same pattern layer was formed. It was irradiated with ultraviolet light and cured under the following conditions.

On the other side @1], an electron beam curable resin composition having the same composition as in Example 1 was applied, laminated onto an aluminum plate, and irradiated with an electron beam under the same conditions to cure. A decorative material with a blue background gave good results.

patent applicant Toyo Ink Manufacturing Co., Ltd.

Claims (1)

[Scope of Claims] 1. A decorative sheet comprising a protective coating layer, a pattern layer, an adhesive layer if necessary, a plastic film, and a radiation-curable adhesive layer. 2. The decorative sheet according to claim 1, wherein the protective coating layer is a curable resin layer. 3. The decorative sheet according to claim 2, wherein the protective coating layer is a radiation-curable resin layer. 4. A protective coating layer, a pattern layer, an adhesive layer if necessary, and a plasti/film surface made of plastic and film are laminated to a base material via a radiation-curable adhesive layer 5, and cross-linked by radiation irradiation. A method for producing decorative materials characterized by hardening.